JP2022025429A - Method for using composition comprising carboxylic acid ester, lithography composition comprising carboxylic acid ester, and method for manufacturing resist pattern - Google Patents

Abstract

To provide a method to reduce standing waves in a lithography process.SOLUTION: The present invention discloses a method for using a composition comprising a carboxylic acid ester (A) having a specific structure to reduce standing waves in a lithography process.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method of using a composition comprising a carboxylic acid ester to reduce standing waves in a lithography process. The present invention also relates to a lithography composition containing a carboxylic acid ester, and a method for producing a resist pattern and a device using the lithography composition.

In recent years, there is an increasing need for high integration of LSI, and miniaturization of patterns is required. In order to meet such needs, a lithography process using a short wavelength KrF excimer laser (248 nm), ArF excimer laser (193 nm), extreme ultraviolet (EUV; 13 nm), X-rays, electron beams, etc. has been put into practical use. It is going on. In order to cope with such miniaturization of the resist pattern, a photosensitive resin composition used as a resist in the microfabrication is also required to have high resolution. A finer pattern can be formed by exposing with light of a short wavelength, but high dimensional accuracy is required.
For example, there is also a study of suppressing fine irregularities on the resist surface by including a specific acid generator in the resist composition itself (Patent Document 1).

In the lithography process, a resist pattern is formed by exposing and developing the resist. It is known that at the time of exposure, the incident light on the resist and the reflected light from the substrate or the air interface interfere with each other to generate a standing wave. The generation of standing waves reduces the pattern dimensional accuracy. There are attempts to form antireflection films on the upper and / or lower layers of the resist to reduce standing waves.

Japanese Unexamined Patent Publication No. 11-12507

FIG. 1 is a schematic diagram showing a cross-sectional shape of a negative resist pattern when affected by a standing wave. FIG. 2 is a schematic cross-sectional system of a negative resist pattern when it is not affected by a standing wave.

The inventor focused on controlling the movement of acids in the chemical process of microfabrication. For example, even if an antireflection film is formed on a substrate in a lithography process and a resist film is formed on the substrate for exposure, standing waves may remain, and a further method is required. Further, since the lower antireflection film needs to be removed after the resist pattern is formed, it may not be usable in the process or it may be necessary to take another measure.
The inventor considered that there were still one or more issues that needed improvement. They include, for example; reduce the standing wave in the lithography process; reduce the standing wave in the resist pattern; suppress the non-uniformity of the resist pattern width; suppress the pattern collapse of the resist pattern; good shape. Obtain a resist pattern; Obtain a resist film with good sensitivity; Obtain a resist film with good resolution; Obtain a finer pattern; Control the movement of acid in the chemical process; Suppress the movement rate of acid in the chemical process; Lithography Improve process yield.

Ｒ^１はＣ_１－１０アルキル、または－ＯＲ^１’であり、
Ｒ^２は－ＯＲ^２’であり、
Ｒ^１’およびＲ^２’はそれぞれ独立にＣ_１－２０炭化水素であり、
Ｒ^３およびＲ^４はそれぞれ独立にＨまたはＣ_１－１０アルキルであり、
Ｒ^１とＲ^３もしくはＲ^４、またはＲ^２とＲ^３もしくはＲ^４が結合し、飽和または不飽和の炭化水素環を形成してもよく、
ｎ１は１または２である：
ただし、ｎ１＝１のとき、Ｒ^１またはＲ^１’、およびＲ^２’のうちの少なくとも一方がＣ_３－２０炭化水素である。 The present invention provides a method of using a composition comprising a carboxylic acid ester (A) in order to reduce standing waves in a lithography process.
Here, the carboxylic acid ester (A) is represented by the formula (a).

R ¹ is C _1-10 alkyl, or -OR ¹ ',
R ² is -OR ^2'and
R _{1'and R 2'are independent C 1-20} ^{hydrocarbons ,} respectively.
R ³ and R ⁴ are independently H or C _1-10 alkyl, respectively.
R ¹ and R ³ or R ⁴ or R ² and R ³ or R ⁴ may combine to form a saturated or unsaturated hydrocarbon ring.
n1 is 1 or 2:
However, when n1 = 1, at least ^one of R ¹ or R ^1'and R 2'is a C _3-20 hydrocarbon.

Ｒ^１はＣ_１－１０アルキル、または－ＯＲ^１’であり、
Ｒ^２は－ＯＲ^２’であり、
Ｒ^１’およびＲ^２’はそれぞれ独立にＣ_１－２０炭化水素であり、
Ｒ^３およびＲ^４はそれぞれ独立にＨまたはＣ_１－１０アルキルであり、
Ｒ^１とＲ^３もしくはＲ^４、またはＲ^２とＲ^３もしくはＲ^４が結合し、飽和または不飽和の炭化水素環を形成してもよく、
ｎ１は１または２である：
ただし、ｎ１＝１のとき、Ｒ^１またはＲ^１’、およびＲ^２’のうちの少なくとも一方がＣ_３－２０炭化水素である。 The lithographic composition according to the present invention is
It comprises a carboxylic acid ester (A) and a solvent (B).
Here, the carboxylic acid ester (A) is represented by the formula (a).

R ¹ is C _1-10 alkyl, or -OR ¹ ',
R ² is -OR ^2'and
R _{1'and R 2'are independent C 1-20} ^{hydrocarbons ,} respectively.
R ³ and R ⁴ are independently H or C _1-10 alkyl, respectively.
R ¹ and R ³ or R ⁴ or R ² and R ³ or R ⁴ may combine to form a saturated or unsaturated hydrocarbon ring.
n1 is 1 or 2:
However, when n1 = 1, at least ^one of R ¹ or R ^1'and R 2'is a C _3-20 hydrocarbon.

The method for producing a film according to the present invention includes the following steps.
(1) The above lithography composition is applied above the substrate;
(2) A film is formed from the lithography composition by reducing pressure and / or heating.

According to the present invention, one or more of the following effects can be desired.
The inventor considered that there were still one or more issues that needed improvement. They include, for example; reduce the standing wave in the lithography process; reduce the standing wave in the resist pattern; suppress the non-uniformity of the resist pattern width; suppress the pattern collapse of the resist pattern; good shape. Obtain a resist pattern; Obtain a resist film with good sensitivity; Obtain a resist film with good resolution; Obtain a finer pattern; Control the movement of acid in the chemical process; Suppress the movement rate of acid in the chemical process; Lithography Improve process yield.

The embodiments of the present invention will be described in detail as follows.

Definitions The definitions and examples provided in this paragraph are followed, unless otherwise specified herein.
The singular includes the plural, and "one" and "that" mean "at least one." An element of a concept can be expressed by a plurality of species, and when the amount (eg, mass% or mol%) is described, the amount means the sum of the plurality of species.
"And / or" includes all combinations of elements and also includes single use.
When the numerical range is indicated by using "-" or "-", these include both endpoints and the unit is common. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.
Descriptions such as "C _x-y ", "C _x -C _y " and "C _x " mean the number of carbons in the molecule or substituent. For example, C _1-6 alkyl means an alkyl chain having 1 or more and 6 or less carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).
If the polymer has multiple repeating units, these repeating units will copolymerize. These copolymers may be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When a polymer or resin is indicated by a structural formula, n, m, etc., which are also written in parentheses, indicate the number of repetitions.
The unit of temperature is Celsius. For example, 20 degrees means 20 degrees Celsius.
The additive refers to the compound itself having the function (for example, in the case of a base generator, the compound itself that generates a base). It is also possible that the compound is dissolved or dispersed in a solvent and added to the composition. As one embodiment of the present invention, such a solvent is preferably contained in the composition according to the present invention as the solvent (B) or other components.

<Method of using a composition containing a carboxylic acid ester>
The present invention relates to a method of using a composition containing a carboxylic acid ester (A) (hereinafter, may be referred to as "composition used in the present invention") in order to reduce standing waves in a lithography process. It is a thing.
Preferably, the composition used in the present invention is applied above the substrate and used to form a film. According to the present invention, since the standing wave can be reduced, the lower layer antireflection film may not be formed on the lower layer of the composition used in the present invention. Therefore, it is also a preferred embodiment of the present invention to apply the composition used in the present invention without forming the lower antireflection film. Since the effect of further reducing standing waves can be further exerted when the lower layer antireflection film is formed, the present invention can be used even when the lower layer antireflection film is formed. The composition of the method of use of the present invention is preferably a lithography composition described later.

ここで、
Ｒ^１はＣ_１－１０アルキル、または－ＯＲ^１’であり；好適にはＣ_１－１０アルキルであり；より好適にはＣ_１－５アルキルである。前記Ｃ_１－５アルキルは、好適にはメチル、エチル、イソプロピル、ｎ－ブチルまたはｔ－ブチルであり；より好適にはメチルまたはｔ－ブチルであり；さらに好適にはメチルである。ｎ１＝２である場合、Ｒ^１は－ＯＲ^１’であることが好適である。
Ｒ^２は－ＯＲ^２’である。
Ｒ^１’およびＲ^２’はそれぞれ独立にＣ_１－２０炭化水素である。
Ｒ^１’は、好適にはＣ_１－５アルキルであり；より好適にはメチルまたはエチルであり；さらに好適にはメチルである。
Ｒ^２’は、好適にはＣ_３－２０炭化水素であり；より好適にはＣ_３－２０アルキル、Ｃ_６－２０アリールまたはＣ_６－２０アリールアルキルであり；さらに好適にはイソプロピル、ｓｅｃ－ブチル、ｔ－ブチル、ｎ－ブチル、ｎ－へプチルまたはベンジルであり；よりさらに好適には、イソプロピル、ｔ－ブチルまたはベンジルである。
理論に拘束されないが、－ＯＲ^２’において、酸素に隣接する隣接する炭素は第三級炭素原子であることが好ましい。これは、第三級炭素原子は脱離しやすく、酸の移動速度を下げることに貢献すると考えられる。
別の態様として、ｎ１＝２のとき、Ｒ^２’は好適にはＣ_１－５アルキルであり；より好適にはメチルまたはエチルであり；さらに好適にはメチルである。
Ｒ^３およびＲ^４はそれぞれ独立にＨまたはＣ_１－１０アルキルであり；好適にはＨまたはＣ_１－５アルキルであり；より好適にはＨ、メチルまたはｔ－ブチルであり；さらに好適には共にＨである。ｎ１＝２のとき、Ｒ^３は１つのカルボン酸エステル（Ａ）に二度出現するが、これら２つのＲ^３は互いに同じでも異なっていても良く；同じであることが好適である。Ｒ^４も同様である。
Ｒ^１とＲ^３もしくはＲ^４、またはＲ^２とＲ^３もしくはＲ^４が結合し、飽和または不飽和の炭化水素環を形成してもよい。ｎ１＝２のとき、ｎ１が付記された（ＣＲ^３Ｒ^４－Ｃ（＝Ｏ）－）が二回繰り返され、Ｒ^３とＲ^４は二度出現するが、この場合、前記結合は近い方の基と結合することが好適である。例えば、２つのＲ^３のうち、Ｒ^１に近い方のＲ^３がＲ^１と結合することが好ましい。Ｒ^１とＲ^３またはＲ^４が結合しないことが、本発明の好適な態様である。Ｒ^２とＲ^３またはＲ^４が結合しないことが本発明の好適な態様である。
ｎ１は１または２であり；好適にはｎ１＝１である。本発明の別の態様として、ｎ１＝２も好適である。
ｎ１＝１のとき、Ｒ^１またはＲ^１’、およびＲ^２’のうちの少なくとも一方がＣ_３－２０炭化水素であり；好適にはＲ^２’がＣ_３－２０炭化水素である。 Carboxylic acid ester (A)
The carboxylic acid ester (A) (hereinafter, may be referred to as a component (A); the same applies to the following (B) described later) is represented by the formula (a).

here,
R ¹ is C _1-10 alkyl, or −OR ¹ ′; preferably C _1-10 alkyl; more preferably C _1-5 alkyl. The C _1-5 alkyl is preferably methyl, ethyl, isopropyl, n-butyl or t-butyl; more preferably methyl or t-butyl; more preferably methyl. When n1 = 2, it is preferable that R ¹ is −OR ¹ ′.
R ² is −OR ² '.
R _{1'and R 2'are independent C 1-20} ^{hydrocarbons ,} respectively.
R _{1'is preferably C 1-5} ^alkyl ; more preferably methyl or ethyl; even more preferably methyl.
^R2'is preferably a C _3-20 hydrocarbon; more preferably C _3-20 alkyl, C _6-20 aryl or C _6-20 aryl alkyl; more preferably isopropyl, sec-. Butyl, t-butyl, n-butyl, n-heptyl or benzyl; more preferably isopropyl, t-butyl or benzyl.
Without being bound by theory, in -OR ² ', the adjacent carbon adjacent to oxygen is preferably a tertiary carbon atom. It is considered that this is because the tertiary carbon atom is easily desorbed and contributes to lowering the transfer rate of the acid.
In another embodiment, when n1 = ² , R2'is preferably C _1-5 alkyl; more preferably methyl or ethyl; even more preferably methyl.
R ³ and R ⁴ are independently H or C _1-10 alkyl, respectively; preferably H or C _1-5 alkyl; more preferably H, methyl or t-butyl; more preferably. Both are H. When n1 = 2, R ³ appears twice in one carboxylic acid ester (A), but these two R ^3s may be the same or different from each other; preferably the same. The same applies to ^R4 .
R ¹ and R ³ or R ⁴ or R ² and R ³ or R ⁴ may combine to form a saturated or unsaturated hydrocarbon ring. When n1 = 2, (CR ³ R ⁴ -C (= O)-) with n1 added is repeated twice, and R ³ and R ⁴ appear twice, but in this case, the bond is closer. It is preferable to bond with the group of. For example, of the two ^{R3s ,} the ^one closer to ^R1 is preferably bound to R1. It is a preferred embodiment of the present invention that R ¹ and R ³ or R ⁴ do not bind. It is a preferred embodiment of the present invention that R ² and R ³ or R ⁴ do not bind.
n1 is 1 or 2; preferably n1 = 1. As another aspect of the present invention, n1 = 2 is also suitable.
When n1 = 1, at least ^one of R ¹ or R ^1'and R 2'is a C _3-20 hydrocarbon; preferably R ^2'is a C _3-20 hydrocarbon.

ここで、
Ｒ^１１はＣ_１－５アルキルであり；好ましくはメチルである。
Ｒ^１２はＣ_３－２０炭化水素であり；好ましくはＣ_３－７アルキルであり；より好ましくはイソプロピル、ｓｅｃ－ブチル、ｔ－ブチル、ｎ－ブチルまたはｎ－へプチルであり；さらに好ましくはイソプロピルまたはｔ－ブチルであり；よりさらに好ましくはｔ－ブチルである。Ｒ^１２において酸素に隣接する炭素は第三級炭素原子であることが好ましい。
Ｒ^１３およびＲ^１４はそれぞれ独立にＨまたはＣ_１－５アルキルであり；好ましくはともにＨである。 Preferably, the carboxylic acid ester (A) is represented by the formula (a1).

here,
R ¹¹ is C _1-5 alkyl; preferably methyl.
R ¹² is a C _3-20 hydrocarbon; preferably C _3-7 alkyl; more preferably isopropyl, sec-butyl, t-butyl, n-butyl or n-heptyl; even more preferably isopropyl. Or t-butyl; even more preferably t-butyl. In R ¹² , the carbon adjacent to oxygen is preferably a tertiary carbon atom.
R ¹³ and R ¹⁴ are independently H or C _1-5 alkyl, respectively; preferably both are H.

Although there is no intention of limiting the present invention, specific examples of the carboxylic acid ester (A) include the following. When n1 = 1 in the formula (a), or the carboxylic acid ester (A) represented by the formula (a1) is applicable.

ここで、
Ｒ^２１およびＲ^２２はＣ_１－５アルキル、好ましくはメチルまたはエチルであり、
Ｒ^２３、Ｒ^２４、Ｒ^２５、およびＲ^２６はそれぞれ独立にＨまたはＣ_１－５アルキル、好ましくはＨであり、より好ましくは全てがＨである。 As one embodiment of the present invention, the carboxylic acid ester (A) is represented by the formula (a2).

here,
R ²¹ and R ²² are C _1-5 alkyl, preferably methyl or ethyl, and
R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are independently H or C _1-5 alkyl, preferably H, and more preferably all H.

Although there is no intention of limiting the present invention, specific examples of the carboxylic acid ester (A) include the following. When n1 = 2 in the formula (a), or the carboxylic acid ester (A) represented by the formula (a2) is applicable.

The following compound is an example of the carboxylic acid ester (A) of the present invention. The following compound can be represented by the formula (a). For example, n1 = 2, R ¹ = C ₃ alkyl (n-propyl), R ² '= t-butyl, both R ³ are H, R ⁴ close to R ¹ is methyl, and R close to R ² . It can be read that ⁴ = H, R ⁴ close to R ¹ and R ¹ are combined to form a saturated hydrocarbon ring (cyclohexyl).

Although not bound by theory, the inclusion of the carboxylic acid ester (A) in the composition used in the present invention can reduce standing waves by producing substances (eg, acid generation) in the composition during the lithography process. It is considered that this is due to contributing to suppressing the moving speed of the acid) generated from the agent (D).

Solvent (B)
The composition used in the present invention preferably contains the solvent (B). The preferred solvent (B) is the same as that described in the subsequent lithography compositions.
The content of the carboxylic acid ester (A) with respect to the solvent (B) is preferably 1.0 to 200% by mass; more preferably 2 to 150% by mass; still more preferably 2.5 to 120% by mass. %; More preferably 2.5 to 50% by mass.

Membrane component (C)
The composition used in the present invention preferably contains a film forming component (C). The preferred film-forming component (C) is the same as that described in the subsequent lithography compositions.
The carboxylic acid ester (A) content is preferably 10 to 3,000% by mass, more preferably 20 to 2,000% by mass, and even more preferably 30 to 1000% by mass, based on the filming component (C). %; More preferably 60-900% by mass.

<Lithography composition>
The lithography composition according to the present invention comprises a carboxylic acid ester (A) represented by the formula (a) and a solvent (B).
In the present invention, the lithography composition refers to a composition used in a photolithography process, for example, for cleaning and film forming applications, specifically, a resist composition, a flattening film, and an antireflection coating on a lower layer. Examples thereof include a film-forming composition, an upper-layer antireflection film-forming composition, a rinsing solution, and a resist mover. The lithographic composition may or may not be removed after the process; it is preferably removed. The material formed from the lithography composition may or may not remain in the final device; it does not preferably remain.
The lithography composition according to the present invention is a lithography film forming composition, more preferably a resist composition. A positive type or a negative type can be used, but a negative type resist composition is preferable.
Further, the lithography composition according to the present invention is preferably a chemically amplified resist composition, more preferably a chemically amplified negative resist composition, and in this case, in addition to the components (A) and (B). Preferably contains a polymer, an acid generator and a cross-linking agent described later.

Carboxylic acid ester (A)
The carboxylic acid ester (A) used in the lithography composition of the present invention is as described above, and the preferred form is the same as described above.
The content of the carboxylic acid ester (A) is preferably 1.0 to 200% by mass; more preferably 2 to 150% by mass; still more preferably 2.5 to 120% by mass based on the solvent (B). It is% by mass; more preferably 2.5 to 50% by mass.

Solvent (B)
The solvent (B) used in the present invention is not particularly limited as long as it can dissolve each component to be blended. Here, it is assumed that the solvent (B) does not contain the solvent corresponding to the above-mentioned carboxylic acid ester (A).
The solvent (B) preferably contains an organic solvent (B1). It is also a preferable aspect that the solvent (B) is composed of only the solvent (B1). The organic solvent (B1) preferably contains a hydrocarbon solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, or a mixture thereof.
Specific examples of the solvent include, for example, water, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-. Octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbensen, i-propylbensen, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbensen, n- Amilnaphthalene, trimethylbenzene, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec -Pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptonol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, Methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2- Methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, acetone, Methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, Trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentandione, acetonylacetone, diacetone alcohol, aceto Phenone, fenchon, ethyl ether, i-propyl ether, n-butyl ether (di-n-butyl ether, DBE), n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyl Dioxorane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono- 2-Ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetra. Ethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono Propyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, Acetate-n-butyl (normal butyl acetate, nBA), i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2 acetate -Ethylhexyl, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl acetate-n- Butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl acetate ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytri acetate Glycol, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate (EL), γ-butyrolactone, n-butyl lactate, n lactate -Amil, diethyl malonate, dimethyl phthalate, diethyl phthalate, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, N-methylformamide, N, N -Dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethylsulfoxide, Sulfolane and 1,3-propanesulton can be mentioned. These solvents can be used alone or in admixture of two or more.
The solvent (B) is preferably PGME, PGMEA, EL, nBA, DBE or a mixture thereof, and more preferably PGME, EL, nBA, DBE or a mixture thereof. PGME, PGMEA or a mixture thereof as the solvent (B) is also suitable as another form of the present invention.

It is also one aspect that the solvent (B) does not substantially contain water in relation to other layers or films. For example, the amount of water in the entire solvent (B) is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and further preferably 0.001% by mass or less. It is also a preferable form that the solvent (B) does not contain water (0% by mass).

The content of the solvent (B) is preferably 10 to 98% by mass; more preferably 20 to 98% by mass; still more preferably 30 to 97% by mass; still more, based on the lithography composition. It is preferably 40 to 95% by mass.

Assuming that the boiling points of the carboxylic acid ester (A) and the solvent (B) are bp _A and bp _B , respectively, and the saturated vapor pressures at 25 ° C. and 1 atm are vpc _A and vpc _B , respectively.
It is preferable that bp _A > bp _B and vpc _A <vpc _B are satisfied.

Membrane component (C)
The lithography composition according to the present invention preferably contains a film forming component (C). In the present invention, the film-forming component (C) refers to a component constituting at least a part of the formed film. The film to be formed does not have to be composed only of the film forming component (C). For example, the film-forming component (C) and the cross-linking agent (E) described later may be combined to form a film. In a preferred embodiment, the film-forming component (C) constitutes most of the film to be formed, for example 60% or more per volume in the film (more preferably 70% or more; more preferably 80% or more; More preferably 90% or more).

The film-forming component (C) preferably contains a polymer (C1). A preferred embodiment of the present invention is that the film-forming component (C) is a polymer (C1).
Examples of the polymer (C1) include novolak derivatives, phenol derivatives, polystyrene derivatives, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonate derivatives, polyvinyl alcohol derivatives, polymethacrylic acid derivatives, and copolymers of combinations thereof.

When the lithography composition according to the present invention is a resist composition, it is preferable that the polymer (C1) is a polymer generally used as a resist composition whose solubility in an alkaline developer changes due to exposure or the like.
When the lithography composition according to the present invention is a chemically amplified positive resist composition, it is preferable that the polymer (C1) reacts with an acid to increase its solubility in a developing solution. Such a polymer has, for example, an acid group protected by a protecting group, and when an acid is added from the outside, the protecting group is removed and the solubility in a developing solution is increased.
When the lithography composition according to the present invention is a chemically amplified negative resist composition, the polymer (C1) is cross-linked between the polymers using an acid generated by exposure as a catalyst, for example, with a cross-linking agent, with respect to the developing solution. It is preferable that the solubility is reduced.
Such a polymer can be arbitrarily selected from those commonly used in lithography methods. Among such polymers, those having at least one repeating unit represented by the following formulas (c1), (c2) and (c3) are preferable. When the lithography composition according to the present invention is a chemically amplified negative resist composition, it is preferable that the polymer (C1) has at least a repeating unit represented by the formula (c1).

ここで、
Ｒ^ｃ１は、Ｈ、Ｃ_１－５アルキル、Ｃ_１－５アルコキシ、または－ＣＯＯＨであり、好ましくはＨまたはメチルであり、より好ましくはＨであり、
Ｒ^ｃ２は、Ｃ_１－５アルキル（これは、－ＣＨ_２－が－Ｏ－によって置きかえられていてもよい）であり、好ましくは、メチル、エチルまたはメトキシであり、より好ましくはメチルであり、
ｍ１は、０～４の数であり、好ましくは０であり、かつ
ｍ２は、１～２の数であり、好ましくは１であり、ｍ１＋ｍ２≦５である。 The repeating unit represented by the formula (c1) is as follows.

here,
R ^c1 is H, C _1-5 alkyl, C _1-5 alkoxy, or —COOH, preferably H or methyl, and more preferably H.
R ^c2 is _{C 1-5} alkyl, which may be replaced by —O—, preferably methyl, ethyl or methoxy, more preferably methyl.
m1 is a number of 0 to 4, preferably 0, and m2 is a number of 1 to 2, preferably 1, m1 + m2 ≦ 5.

Specific examples of the formula (c1) are as follows.

ここで、
Ｒ^ｃ３は、Ｈ、Ｃ_１－５アルキル、Ｃ_１－５アルコキシ、または－ＣＯＯＨであり、好ましくは水素、またはメチルであり、より好ましくは水素である。
Ｒ^ｃ４は、Ｃ_１－５アルキルまたはＣ_１－５アルコキシ（ここで、アルキル、アルコキシに含まれる－ＣＨ_２－が－Ｏ－によって置き換えられていてもよい）であり、より好ましくはＣ_１－５アルコキシ（ここで、アルコキシに含まれる－ＣＨ_２－が－Ｏ－によって置き換えられていてもよい）であり、このとき、ｍ３は１であることが好ましい。この態様におけるＲ^ｃ４として、メトキシ、ｔ－ブチルオキシ、および－Ｏ－ＣＨ（ＣＨ_３）－Ｏ－ＣＨ_２ＣＨ_３が挙げられる。
ｍ３は、０～５の数であり、好ましくは０、１、２、３、４または５であり、より好ましくは０または１である。ｍ３が０であることも好適な一態様である。 The structural unit represented by the formula (c2) is as follows.

here,
R ^c3 is H, C _1-5 alkyl, C _1-5 alkoxy, or —COOH, preferably hydrogen, or methyl, and more preferably hydrogen.
R ^c4 is C _1-5 alkyl or C _1-5 alkoxy (where-CH _2- contained in alkyl, alkoxy may be replaced by -O-), more preferably C _1- . ₅ Alkoxy (here, —CH ₂ − contained in alkoxy may be replaced by —O—), where m3 is preferably 1. Examples of R ^c4 in this embodiment include methoxy, t-butyloxy, and -O-CH (CH ₃ ) -O-CH ₂ CH ₃ .
m3 is a number from 0 to 5, preferably 0, 1, 2, 3, 4 or 5, and more preferably 0 or 1. It is also a preferable aspect that m3 is 0.

Specific examples of the formula (c2) are as follows.

ここで、
Ｒ^ｃ５は、Ｈ、Ｃ_１－５アルキル、Ｃ_１－５アルコキシ、または－ＣＯＯＨであり、より好ましくはＨ、メチル、エチル、メトキシ、または－ＣＯＯＨであり、さらに好ましくは水素またはメチルであり、さらにより好ましくはＨである。
Ｒ^ｃ６は、Ｃ_１－１５アルキルまたはＣ_１－５アルキルエーテルであり、Ｒ^ｃ６は環構造を有していてもよく、好ましくはメチル、イソプロピル、ｔ－ブチル、シクロペンチル、メチルシクロペンチル、エチルシクロペンチル、メチルシクロヘキシル、エチルシクロヘキシル、メチルアダマンチルまたはエチルアダマンチルであり、より好ましくはｔ－ブチル、エチルシクロペンチル、エチルシクロヘキシル、またはエチルアダマンチルであり、さらに好ましくはｔ－ブチルである。 The structural unit represented by the formula (c3) is as follows.

here,
R ^c5 is H, C _1-5 alkyl, C _1-5 alkoxy, or —COOH, more preferably H, methyl, ethyl, methoxy, or —COOH, still more preferably hydrogen or methyl. Even more preferably, it is H.
R ^c6 is a C _1-15 alkyl or C _1-5 alkyl ether, and R ^c6 may have a ring structure, preferably methyl, isopropyl, t-butyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, Methylcyclohexyl, ethylcyclohexyl, methyladamantyl or ethyladamantyl, more preferably t-butyl, ethylcyclopentyl, ethylcyclohexyl, or ethyladamantyl, still more preferably t-butyl.

Specific examples of the formula (c3) are as follows.

Since these constituent units are appropriately blended according to the purpose, their blending ratio is not particularly limited, but it is preferably blended so that the solubility in the alkaline developer is appropriate.
These polymers can also be used in combination of two or more.

The mass average molecular weight (hereinafter sometimes referred to as Mw) of the polymer (C1) is preferably 500 to 100,000; more preferably 1,000 to 50,000; still more preferably 3,000 to 20. It is 000; more preferably 4,000 to 20,000.
In the present invention, Mw can be measured by gel permeation chromatography (GPC). In the same measurement, it is a preferable example to use a GPC column at 40 degrees Celsius, an elution solvent tetrahydrofuran at 0.6 mL / min, and monodisperse polystyrene as a standard.

Based on the film-forming component (C), the content of the carboxylic acid ester (A) is preferably 10 to 3,000% by mass; more preferably 20 to 2,000% by mass; still more preferably 30. It is ~ 1,000% by mass; more preferably 60 to 900% by mass.
The content of the film-forming component (C) is preferably 2 to 40% by mass, more preferably 2 to 30% by mass, and even more preferably 3 to 25% by mass, based on the lithography composition. Even more preferably, it is 3 to 20% by mass.

Assuming that the ratios of the repeating units represented by the formulas (c1), (c2) and (c3) are n _c1 , n _c2 and n _c3 , respectively, based on the total number of repeating units in the polymer (C1), the following Is one of the preferred embodiments of the present invention.
n _c1 = 0-100%; more preferably 30-100%; more preferably 50-100%; even more preferably 60-100%.
n _c2 = 0 to 100%; more preferably 0 to 70%; even more preferably 0 to 50%; even more preferably 0 to 40%.
n _c3 = 0 to 50%; more preferably 0 to 40%; even more preferably 0 to 30%; even more preferably 0 to 20%. Another preferred embodiment of the present invention is an embodiment (n _c3 = 0) that does not include the repeating unit represented by the formula (c3).

Acid generator (D)
The lithography composition according to the present invention may contain an acid generator (D). In the present invention, the acid generator refers to the compound itself having an acid generating function. Examples of the acid generator include a photoacid generator (PAG) that generates an acid by exposure and a thermal acid generator (TAG) that generates an acid by heating. When the lithography composition according to the present invention is a chemically amplified resist composition, it is preferable to include a photoacid generator.

Examples of the photoacid generator include sulfonium salts, iodonium salts, sulfonyldiazomethanes, and N-sulfonyloxyimide acid generators. Typical acid generators are shown below, which can be used alone or in admixture of two or more.

Sulfonium salts are salts of sulfonium cations with anions containing carboxylates, sulfonates or imides. Typical sulfonium cations include triphenylsulfonium, (4-methylphenyl) diphenylsulfonium, (4-methoxyphenyl) diphenylsulfonium, tris (4-methoxyphenyl) sulfonium, (4-tert-butylphenyl) diphenylsulfonium, (4-tert-Butoxyphenyl) diphenyl sulfonium, bis (4-tert-butoxyphenyl) phenyl sulfonium, tris (4-tert-butyl phenyl) sulfonium, tris (4-tert-butoxyphenyl) sulfonium, tris (4-methyl) Phenyl) Sulfonium, (4-methoxy-3,5-dimethylphenyl) dimethylsulfonium, (3-tert-butoxyphenyl) diphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl) ) Sulfonium, (3,4-di-tert-butoxyphenyl) diphenylsulfonium, bis (3,4-di-tert-butoxyphenyl) phenylsulfonium, tris (3,4-di-tert-butoxyphenyl) sulfonium, ( 4-Phenoxyphenyl) Diphenyl Sulfonium, (4-Cyclohexylphenyl) Diphenyl Sulfonium, Bis (p-Phenylene) Bis (Diphenyl Sulfonium), Diphenyl (4-thiophenoxyphenyl) Sulfonium, Diphenyl (4-thiophenylphenyl) Sulfonium, Diphenyl (8-thiophenylbiphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl) sulfonium, (4-tert-butoxyphenyl) bis (4-dimethyl) Aminophenyl) Sulfonium, Tris (4-dimethylaminophenyl) Sulfonium, 2-naphthyldiphenylsulfonium, dimethyl (2-naphthyl) sulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexyl Included are cyclohexylmethyl sulfonium, trinaphthyl sulfonium, and tribenzyl sulfonium. Typical sulfonates include trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4- (trifluoromethyl) benzenesulfonate, Included are 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, 4- (4-toluene sulfonyloxy) benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecylbenzene sulfonate, butane sulfonate, and methane sulfonate. Typical imides include bis (perfluoromethanesulfonyl) imide, bis (perfluoroethanesulfonyl) imide, bis (perfluorobutanesulfonyl) imide, bis (perfluorobutanesulfonyloxy) imide, and bis [perfluoro (2). -Ethoxyethane) sulfonyl] imide, and N, N-hexafluoropropane-1,3-disulfonylimide. Typical other anions include 3-oxo-3H-1,2-benzothiazole-2-id, 1,1-dioxide, tris [(trifluoromethyl) sulfonyl] methanide and tris [(perfluorobutyl). Sulfonyl] methaneid can be mentioned. Fluorocarbon-containing anions are preferred. Includes sulfonium salts based on the combination of the above examples.

The iodonium salt is a salt of an anion containing a sulfonate and an imide and an iodonium cation. Typical iodonium cations include diphenyliodonium, bis (4-tert-butylphenyl) iodonium, bis (4-tert-pentylphenyl) iodonium, 4-tert-butoxyphenylphenyliodonium, 4-methoxyphenylphenyliodonium and the like. Aryliodonium cations can be mentioned. Typical sulfonates include trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4- (trifluoromethyl) benzenesulfonate, Included are 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, 4- (4-toluene sulfonyloxy) benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecylbenzene sulfonate, butane sulfonate, and methane sulfonate. Typical imides include bis (perfluoromethanesulfonyl) imide, bis (perfluoroethanesulfonyl) imide, bis (perfluorobutanesulfonyl) imide, bis (perfluorobutanesulfonyloxy) imide, and bis [perfluoro (2). -Ethoxyethane) sulfonyl] imide, and N, N-hexafluoropropane-1,3-disulfonylimide. Typical other anions include 3-oxo-3H-1,2-benzothiazole-2-id, 1,1-dioxide, tris [(trifluoromethyl) sulfonyl] methanide and tris [(perfluorobutyl). Sulfonyl] methaneid can be mentioned. Fluorocarbon-containing anions are preferred. Includes iodonium salts based on the combination of the above examples.

Typical sulfonyl diazomethane compounds include bis (ethylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, bis (2-methylpropylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, and bis ( Cyclohexylsulfonyl) diazomethane, bis (perfluoroisopropylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (2-naphthylsulfonyl) Diazomethane, 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane, 2-naphthylsulfonylbenzoyldiazomethane, 4-methylphenylsulfonyl-2-naphthoyldiazomethane, methylsulfonylbenzoyldiazomethane, and tert-butoxy Examples thereof include bissulfonyldiazomethane compounds such as carbonyl-4-methylphenylsulfonyldiazomethane and sulfonylcarbonyldiazomethane compounds.

Examples of the N-sulfonyloxyimide photoacid generator include a combination of an imide skeleton and a sulfonic acid. Typical imide skeletons include succinic acid imide, naphthalenedicarboxylic acid imide, phthalimide, cyclohexyldicarboxylic acid imide, 5-norbornene-2,3-dicarboxylic acid imide, and 7-oxabicyclo [2.2.1] -5. -Heptene-2,3-dicarboxylic acid imide can be mentioned. Typical sulfonates include trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4- Fluorobenzene sulphonates, toluene sulphonates, benzene sulphonates, naphthalene sulphonates, camphor sulphonates, octane sulphonates, dodecylbenzene sulphonates, butane sulphonates, and methane sulphonates can be mentioned.

Benzoinsulfonate photoacid generators include benzointosylate, benzoinmesylate, and benzoinbutanesulfonate.

Pyrogallol trisulfonate photoacid generators include pyrogallol, fluoroglucolcinol, catechol, resorcinol, and hydroquinone, of which all hydroxyl groups are trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctane. Sulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate , Butane sulfonate, or methane sulfonate.

Examples of the nitrobenzylsulfonate photoacid generator include 2,4-dinitrobenzylsulfonates, 2-nitrobenzylsulfonates, and 2,6-dinitrobenzylsulfonates, typically trifluoromethanesulfonates and nonafluorobutane. Ssulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camphor sulfonate, Examples include sulfonates including octane sulfonate, dodecylbenzene sulfonate, butane sulfonate, and methane sulfonate. Also useful are similar nitrobenzyl sulfonate compounds in which the nitro group on the benzyl side is replaced with trifluoromethyl.

Examples of the sulfone photoacid generator include bis (phenylsulfonyl) methane, bis (4-methylphenylsulfonyl) methane, bis (2-naphthylsulfonyl) methane, 2,2-bis (phenylsulfonyl) propane, and 2,2-bis. (4-Methylphenylsulfonyl) propane, 2,2-bis (2-naphthylsulfonyl) propane, 2-methyl-2- (p-toluenesulfonyl) propiophenone, 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) ) Propane and 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one.

Examples of the photoacid generator in the form of a glyoxime derivative include bis-O- (p-tolnsulfonyl) -α-dimethylglyoxime, bis-O- (p-tolnsulfonyl) -α-diphenylglyoxime, and bis-O-. (P-toluenesulfonyl) -α-dicyclohexylglycimme, bis-O- (p-toluenesulfonyl) -2,3-pentandiondioneglycim, bis-O- (p-toluenesulfonyl) -2-methyl-3, 4-Pentanedioneglyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl) ) -Α-Dicyclohexylglycoxime, bis-O- (n-butanesulfonyl) -2,3-pentanedioneglioxime, bis-O- (n-butanesulfonyl) -2-methyl-3,4-pentanediongly Oxyme, bis-O- (methanesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-O- (1,1,1-trifluoroethanesulfonyl)- α-Dimethylglyoxime, bis-O- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-O- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-O- (cyclohexylsulfonyl) -α -Dimethylglyoxime, bis-O- (benzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-tert-butylbenzenesulfonyl) )-Α-Dimethylglyoxime, bis-O- (xylenesulfonyl) -α-dimethylglyoxime, and bis-O- (kanfersulfonyl) -α-dimethylglyoxime.

Among these, preferred PAGs are sulfonium salts, iodonium salts, and N-sulfonyloxyimides.

The optimum anion of the generated acid depends on factors such as the ease of cleavage of the acid unstable group in the polymer, but non-volatile and extremely non-diffusible anions are generally selected. To. Suitable anions include benzene sulfonic acid, toluene sulfonic acid, 4- (4-toluene sulfonyloxy) benzene sulfonic acid, pentafluorobenzene sulfonic acid, 2,2,2-trifluoroethane sulfonic acid, nonafluorobutane sulfonic acid. , Heptadecafluorooctane sulfonic acid, camphor sulfonic acid, disulfonic acid, sulfonylimide, and sulfonylmethanide anions.

Examples of thermoacid generators are metal-free sulfonium and iodonium salts, such as triarylsulfonium, dialkylarylsulfonium, and diarylalkylsulfonium salts, which are strongly non-requiring nucleic acids, alkylaryliodonium, diaryliodonium, which are strongly non-requiring nucleic acids. Salts; and strong non-sulphonium ammonium, alkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium salts. Covalent thermoacid generators are also considered useful additives, such as 2-nitrobenzyl esters of alkyl or aryl sulfonic acids, and other sulfonic acids that thermally decompose to yield free sulfonic acids. There is an ester. Examples are diaryliodonium perfluoroalkyl sulfonate, diaryliodonium tris (fluoroalkylsulfonyl) methide, diaryliodonium bis (fluoroalkylsulfonyl) methide, diaryliodonium bis (fluoroalkylsulfonyl) imide, diaryliodonium quaternary ammonium perfluoroalkyl. It is a sulfonate. Examples of unstable esters are 2-nitrobenzyl tosylate, 2,4-dinitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, 4-nitrobenzyl tosylate; 2-trifluoromethyl-6-nitrobenzyl. Benzene sulfonates such as 4-chlorobenzene sulfonate, 2-trifluoromethyl-6-nitrobenzyl 4-nitrobenzene sulfonate; phenolic sulfonate esters such as phenyl 4-methoxybenzene sulfonate; quaternary ammonium tris (fluoroalkylsulfonyl) methides, and A quaternary alkylammonium bis (fluoroalkylsulfonyl) imide, an alkylammonium salt of an organic acid, for example a triethylammonium salt of 10-camper sulfonic acid. Various aromatic (anthracene, naphthalene, or benzene derivatives) sulfonic acid amine salts are used in US Pat. Nos. 3,474,054, 4,200,729, 4,251,665, and 5,187. , 019 disclosed can also be used as a TAG.

The acid generator (D) may be two or more kinds of compounds.

The content of the acid generator (D) is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, and even more preferably 1 based on the film-forming component (C). It is 0.0 to 5% by mass; more preferably 1.5 to 4% by mass.

Crosslinking agent (E)
The lithography composition according to the present invention may contain a cross-linking agent (E). In the present invention, the cross-linking agent refers to the compound itself having a cross-linking function. The cross-linking agent is not particularly limited as long as it cross-links the component (C) within and / or between molecules.

Examples of the cross-linking agent include a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, an epoxy compound, a thioepoxy compound, an isocyanate compound and an azide substituted with at least one group selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group. Examples thereof include compounds containing double bonds such as compounds and alkenyl ether groups. A compound containing a hydroxy group is also used as a cross-linking agent.
Examples of the epoxy compound include tris (2,3-epoxypropyl) isocyanate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and trimethylolethane triglycidyl ether. Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, and hexamethylol melamine, which are compounds in which 1 to 6 methylol groups are methoxymethylated and a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, and hexamethylol melamine. Examples thereof include compounds in which 1 to 6 methylol groups are acyloxymethylated or a mixture thereof. Examples of the guanamine compound include a compound in which 1 to 4 methylol groups of tetramethylol guanamine, tetramethoxymethyl guanamine, and tetramethylol guanamine are methoxymethylated and a mixture thereof, and one of tetramethoxyethyl guanamine, tetraacyloxyguanamine, and tetramethylol guanamine. Examples thereof include compounds in which up to 4 methylol groups are acyloxymethylated and mixtures thereof. Examples of the glycol uryl compound include tetramethylol glycol uryl, tetramethoxyglycol uryl, tetramethoxymethyl glycol uryl, and a compound in which 1 to 4 methylol groups of tetramethylol glycol uryl are methoxymethyl-based, or a mixture thereof, or a mixture thereof. Examples thereof include a compound in which 1 to 4 methylol groups of the above are acyloxymethylated or a mixture thereof. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethyl-based, or a mixture thereof, and tetramethoxyethyl urea. Examples of the compound containing an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, and neopentyl glycol divinyl ether. Examples thereof include trimethylol propanetrivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trimethylol propanetrivinyl ether.

Examples of the cross-linking agent containing a hydroxy group include the following.

The cross-linking temperature at the time of forming the film is preferably 50 to 230 ° C, more preferably 80 to 220 ° C, and even more preferably 80 to 190 ° C.

The content of the cross-linking agent (E) is preferably 3 to 30% by mass, more preferably 5 to 20% by mass, based on the film-forming component (C).

Basic compound (F)
The lithography composition according to the present invention can further contain the basic compound (F). The basic compound (F) has an effect of neutralizing the acid generated in the exposed portion and suppressing the environmental influence.
In addition to the above effects, the basic compound also has an effect of suppressing the deactivation of the acid on the film surface due to the amine component contained in the air.

The basic compound (F) is preferably ammonia, a primary aliphatic amine of C _1-16 , a secondary aliphatic amine of C _2-32 , a tertiary aliphatic amine of C _3-48 , and C ₆ It is selected from the group consisting of _-30 aromatic amines and C _5-30 heterocyclic amines, as well as derivatives thereof.

Specific examples of the basic compound include ammonia, ethylamine, n-octylamine, ethylenediamine, triethylamine, triethanolamine, tripropylamine, tributylamine, triisopropanolamine, diethylamine, and tris [2- (2-methoxyethoxy) ethyl. ] Amine, 1,8-diazabicyclo [5.4.0] Undecene-7, 1,5-diazabicyclo [4.3.0] Nonen-5, 7-methyl-1,5,7-triazabicyclo [4] .4.0] Deca-5-ene and 1,5,7-triazabicyclo [4.4.0] Deca-5-ene.

The molecular weight of the basic compound (F) is preferably 17 to 500, more preferably 100 to 350.

The content of the basic compound (F) is preferably 0.01 to 1.0% by mass, more preferably 0.20 to 0.8% by mass, based on the filming component (C); More preferably, it is 0.20 to 0.5% by mass. Considering the storage stability of the composition, it is also a preferable form that it does not contain the basic compound (F) (0.00% by mass).

Surfactant (G)
The lithography composition according to the present invention preferably contains a surfactant (G). By containing a surfactant, the coatability can be improved. Examples of the surfactant that can be used in the present invention include (I) anionic surfactant, (II) cationic surfactant, and (III) nonionic surfactant, and more specifically. (I) Alkyl sulfonate, Alkyl benzene sulfonic acid, and Alkyl benzene sulfonate, (II) Lauryl pyridinium chloride, and Lauryl methyl ammonium chloride, and (III) Polyoxyethylene octyl ether, Polyoxyethylene lauryl ether, Polyoxyethylene acetylenic. Glycol ethers, fluorine-containing surfactants (eg Florard (3M), Megafuck (DIC), Sulflon (Asahi Glass), and organic siloxane surfactants (eg KF-53, KP341 (Shinetsu Chemical Industry)) can be mentioned. ..

These surfactants can be used alone or in admixture of two or more. The content of the surfactant (G) is preferably 0.05 to 0.5% by mass, more preferably 0.09 to 0.2% by mass, based on the film-forming component (C).

Additive (H)
The lithography composition according to the present invention can contain an additive (H) other than the components (A) to (G). The additive (H) preferably comprises a plasticizer, a dye, a contrast enhancer, an acid, a radical generator, a substrate adhesion enhancer, an antifoaming agent, or a mixture thereof.
The content of the additive (H) (in the case of a plurality thereof, the sum thereof) is preferably 0.1 to 20% by mass; more preferably 0.1 to 10% by mass; further, based on the composition. It is preferably 1 to 5% by mass. It is also one of the forms of the present invention that the composition according to the present invention does not contain the additive (H) (0.0% by mass).

<Membrane manufacturing method>
The method for producing a film according to the present invention includes the following steps.
(1) The lithography composition according to the present invention is applied above the substrate;
(2) A film is formed from the lithography composition by depressurization and / or heating.
Hereinafter, the numbers in parentheses indicate the order of the processes. For example, when the steps (1), (2), and (3) are described, the order of the steps is as described above.
In the present invention, the membrane is dried or cured and includes, for example, a resist membrane.
According to the present invention, since the influence of standing waves can be reduced during film formation, an antireflection film (for example, a resist underlayer antireflection film) is not formed above the substrate before applying the lithography composition. May be good. Those who do not have an antireflection film formed under the lithography composition because it needs to be removed and the manufacturing process becomes simpler when an antireflection film is formed under the lithography composition. Is preferable.

Hereinafter, one aspect of the production method according to the present invention will be described.
The lithography composition according to the present invention is applied on a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate, an ITO substrate, etc.) by an appropriate method. Here, in the present invention, the upper part includes a case where it is formed directly above and a case where it is formed via another layer. For example, a flattening film may be formed directly above the substrate, and the composition according to the present invention may be applied directly above the flattening film. The application method is not particularly limited, and examples thereof include a method of application by a spinner and a coater. After coating, the film according to the present invention is formed by reducing the pressure and / or heating. The film may be formed by rotating the substrate at high speed without heating and evaporating the solvent. When the lithography composition according to the present invention is a resist composition, heating is performed, for example, by a hot plate. The heating temperature is preferably 80 to 250 ° C; more preferably 80 to 200 ° C; still more preferably 90 to 180 ° C. The heating time is preferably 30 to 600 seconds; more preferably 30 to 300 seconds; still more preferably 60 to 180 seconds. The heating is preferably carried out in an atmosphere or a nitrogen gas atmosphere.
The film thickness of the resist film varies depending on the exposure wavelength, but is preferably 100 to 50,000 nm. When the exposure uses a KrF excimer laser, the film thickness of the resist film is preferably 100 to 5,000 nm; more preferably 100 to 1,000 nm; still more preferably 400 to 600 nm.

When the lithography composition according to the present invention is a resist composition, the method for producing a resist pattern according to the present invention includes the following steps.
A film is formed using the lithography composition by the method described above.
(3) Exposing the film with radiation
(4) The film is developed to form a resist pattern.

The film formed using the resist composition is exposed through a predetermined mask. The wavelength of the light used for the exposure is not particularly limited, but it is preferable to expose with light having a wavelength of 13.5 to 365 nm. Specifically, i-line (wavelength nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), extreme ultraviolet rays (wavelength 13.5 nm) and the like can be used, preferably KrF excimer laser. Is. These wavelengths allow a range of ± 1%. After the exposure, if necessary, post-exposure heating can be performed. The temperature of post-exposure heating is preferably 80 to 150 ° C, more preferably 100 to 140 ° C, and the heating time is 0.3 to 5 minutes, preferably 0.5 to 2 minutes.
The exposed film is developed with a developer. The developer used is preferably a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution. The temperature of the developing solution is preferably 5 to 50 ° C., more preferably 25 to 40 ° C., and the developing time is preferably 10 to 300 seconds, more preferably 30 to 60 seconds.
By using such a developer, the film can be easily dissolved and removed at room temperature. Further, for example, a surfactant can be added to these developers.
When a negative resist composition is used, the positive photoresist layer in the unexposed portion is removed by development to form a resist pattern. It is also possible to further miniaturize this resist pattern by using, for example, a shrink material.

FIG. 1 is a schematic diagram showing a cross-sectional shape of a negative resist pattern when affected by a standing wave. The resist pattern 1 is formed on the substrate 2. When a corrugated shape having a large amplitude is formed in the cross section in this way, the resist top shape fluctuates greatly with a slight difference in film thickness, and the dimensional accuracy deteriorates. Therefore, it is preferable that such an amplitude is small. .. Here, from the point where the substrate and the resist pattern are in contact with each other, the first point where the thickness of the resist pattern becomes maximum is set as the antinode 3, and the point where the thickness of the resist pattern immediately above it is the minimum is defined. Let it be section 4. The distance between the abdomen and the segment in the direction parallel to the substrate is called the internode distance 5. It is preferable that the distance between the abdominal segments is small, and specifically, the distance between the abdominal segments / the target pattern width (hereinafter, may be referred to as a standing wave index) is preferably less than 10%. , More preferably 5% or less. Here, the target pattern width may be the width of the top of the resist assuming that it is not affected by the standing wave. By reducing the standing wave that appears in the resist pattern, the shape may be different from the intended one, or the cut may be made, which suppresses the pattern collapse and facilitates the stable formation of a finer pattern.
FIG. 2 is a schematic diagram of the cross-sectional shape of the negative resist pattern when it is not affected by the standing wave. In the negative resist, since the polymer is insolubilized via the acid generated by the exposure, it is difficult for light to reach the lower part and the acid generation is less than the upper part, and the lower part is less insolubilized than the upper part. Therefore, the formed pattern tends to have a reverse taper shape. In FIG. 2, there are no antinodes and nodes, in which case the standing wave index is considered to be zero.

The method for manufacturing a metal pattern according to the present invention is
A resist pattern is formed by the method described above, and the resist pattern is formed.
(5a) A metal layer is formed on the resist pattern;
(6a) Includes removing the remaining resist patterns and the metal layers above them. Following the steps (1) to (4), the steps (5a) and (6a) are performed. The order of the processes is the same as the previous term.
The metal layer is formed by forming a metal such as gold or copper (which may be a metal oxide or the like) by, for example, thin-film deposition or spalling. After that, the resist pattern can be formed by removing the resist pattern together with the metal formed on the resist pattern with a stripping solution. The stripping solution is not particularly limited as long as it is used as a stripping solution for resist, and for example, N-methylpyrrolidone (NMP), acetone, or an alkaline solution is used. When the resist according to the present invention is a negative type, it tends to have a reverse taper shape as described above. In the case of the reverse taper, the metal on the resist pattern and the metal formed in the portion where the resist pattern is not formed are separated from each other, so that the metal can be easily peeled off.

The method for manufacturing a pattern substrate according to the present invention is as follows.
A resist pattern is formed by the method described above, and the resist pattern is formed.
(5b) Etching with the resist pattern as a mask;
(6b) Includes processing the substrate. The etching may be either dry etching or wet etching, and the etching may be performed a plurality of times. Following the steps (1) to (4), the steps (5b) and (6b) are performed. The order of the processes is the same as the previous term.

Further, the method for manufacturing a pattern substrate according to the present invention is as follows.
A resist pattern is formed by the method described above, and the resist pattern is formed.
(5c) Etching the resist pattern;
(5d) Includes etching the substrate. Following the steps (1) to (4), the steps (5c) and (6d) are performed. The order of the processes is the same as the previous term.
Here, the combination of the steps (5c) and (5d) is repeated at least twice; and the substrate is composed of a plurality of Si-containing layers laminated, and at least one Si-containing layer is conductive. At least one Si-containing layer is electrically insulating. Preferably, the conductive Si-containing layer and the electrically insulating Si-containing layer are alternately laminated. Here, the film thickness of the resist film formed from the lithography composition is preferably 0.5 to 200 μm.

Then, if necessary, the substrate is further processed to form the device. For this further processing, known methods can be applied. The method for manufacturing a device according to the present invention includes any of the above methods, and preferably further includes a step of forming wiring on a processed substrate. Examples of the device include a semiconductor element, a liquid crystal display element, an organic EL display element, a plasma display element, and a solar cell element. The device is preferably a semiconductor device.

The present invention will be described below with reference to various examples. The aspect of the present invention is not limited to these examples.

The components used below are shown below.

Ａ１：ｔ－ブチルアセトアセテート（ＴＣＩ）

Ａ２：メチル－４，４－ジメチル－３－オキソバレレート（ＴＣＩ）

Ａ３：イソプロピルアセトアセテート（ＴＣＩ）

Ａ４：ｓ－ブチルアセトアセテート（ＴＣＩ）

Ａ５：ジメチル－１，３－アセトンジカルボキシレート（ＴＣＩ）

Ａ６：ジエチル－１，３－アセトンジカルボキシレート（ＴＣＩ）

The component (A) or comparative compound used is as follows.
Comparative compound CA: Methylacetacetate (Tokyo Chemical Industry, hereafter TCI)

A1: t-Butylacetate acetate (TCI)

A2: Methyl-4,4-dimethyl-3-oxovalerate (TCI)

A3: Isopropylacetate acetate (TCI)

A4: s-Butylacetate acetate (TCI)

A5: Dimethyl-1,3-acetone dicarboxylate (TCI)

A6: Diethyl-1,3-acetone dicarboxylate (TCI)

The component (B) used is as follows.
B1: PGMEA
B2: PGME
B3: EL

Ｃ１－２：ＶＰ－３５００、ｐ－ハイドロキシスチレン、Ｍｗ約５０００（日本曹達）

Ｃ１－３：Ｐｏｌｙ－ＴＺ－ＧＩＪランダムコポリマー、（ｐ－ハイドロキシスチレン（６０）、スチレン（２０）、ｔ－ブチルアクリレート）、Ｍｗ約１２，０００（Ｄｕｐｏｎｔ）

The component (C) used is as follows.
C1-1: CST7030 Random Copolymer (p-hydroxystyrene (70), styrene (30)), Mw approx. 9700 (Maruzen Petrochemical)

C1-2: VP-3500, p-hydroxystyrene, Mw about 5000 (Nippon Soda)

C1-3: Poly-TZ-GIJ random copolymer, (p-hydroxystyrene (60), styrene (20), t-butyl acrylate), Mw about 12,000 (Dupont)

Ｄ２：ＴＰＳ－ＳＡ（東洋合成）

Ｄ３：ＴＰＳ－Ｃ１（ヘレウス）

Ｄ４：ＭＤＴ Ｓｅｎｓｉｔｉｚｅｒ（ヘレウス）

Ｄ５：Ｇａｒｏ ＩＮ－Ｋ（ＤＳＰ五協フード＆ケミカル）

Ｄ６：ＷＰＩ－１６９（富士フィルム和光純薬）

(D) to be used is as follows.
D1: WPAG367 (Fuji Film Wako Pure Chemical Industries, Ltd.)

D2: TPS-SA (Oriental synthesis)

D3: TPS-C1 (Heraeus)

D4: MDT Sensor (Heraeus)

D5: Garo IN-K (DSP Gokyo Food & Chemical)

D6: WPI-169 (Fuji Film Wako Pure Chemical Industries, Ltd.)

The component (E) used is as follows.
E1: DML-POP, Honshu Chemical Industry

The component (F) used is as follows.
F1: Triethanolamine (TCI)
F2: Tris [2- (2-methoxyethoxy) ethyl] amine (TCI)

The component (G) used is the surfactant G1 (MegafacR2011, DIC).

<Preparation of Comparative Example Composition 1>
Solvent B1 (65.1 g) and solvent B2 (27.9 g) are mixed to prepare a B1B2 mixed solvent. To this, 3.710 g of C1-1, 2.474 g of C1-2, 0.577 g of E1, 0.127 g of D1, 0.106 g of D2 and 0.006 g of G1 are added, respectively. Mix the solution at room temperature and visually confirm that the solid component dissolves. Comparative Example Composition 1 is obtained.

<Preparation of Example Compositions 1 to 8 and Comparative Example Compositions 2 to 3>
Examples Compositions 1 to 8 and Comparative Example Compositions 2 to 3 are prepared in the same manner as in the preparation example of Comparative Example Composition 1 except that the components are changed as shown in Tables 1 and 2 below.

<Resist pattern formation example 1>
AZ KrF-17B (Merck Performance Materials, hereinafter referred to as MPM) is spin-coated on the surface of a silicon substrate (SUMCO Corp., 8 inches) and soft-baked at 180 ° C. for 60 seconds to form a 45 nm BARC film. The composition of the example is spin-coated onto the composition and soft-baked at 110 ° C. for 60 seconds to form a resist film having a film thickness of 235 nm on the same substrate. With this configuration, the light reflectance of the KrF line (248 nm) is set to 7%. The obtained substrate is exposed with KrF rays using an exposure apparatus (Canon, FPA-3000EX5). As the exposure mask, a mask having a line: space = 1: 1 and a space of 1.0 μm continuing multiple times and the space gradually decreasing as shown below is used.
1000 nm, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 280 nm, 260 nm, 240 nm, 220 nm, 200 nm, 190 nm, 180 nm, 170 nm, 160 nm, 150 nm, 140 nm, 130 nm, 120 nm, 110 nm, 100 nm.
The substrate is post-exposure baked (PEB) at 100 ° C. for 60 seconds. Then, the resist film is paddle-developed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds. With the paddle developer paddled on the substrate, pure water is started to flow on the substrate, the paddle developer is replaced with pure water while rotating, and spin-dried at 2000 rpm.

<Evaluation of standing wave reduction 1>
Evaluate the reduction of standing waves. Observe the pattern in which the space of the resist pattern formed in the resist pattern forming example 1 corresponds to 150 nm. Sections are prepared from the substrate and observed by SEM (SU8230, Hitachi High-Technologies). The distance between the abdominal segments defined above is measured (Offline CD Measurement Software Version 6.00, Hitachi High-Technologies). The standing wave index is calculated by dividing the distance between the abdomen by the target pattern width. Evaluate according to the following evaluation criteria.
A: Standing wave index is 0% or more and 5% or less B: Standing wave index is greater than 5% and less than 10% C: Standing wave index is 10% or more

比較組成物１で示されるように、ＢＡＲＣを有する場合であっても定在波が完全には防げない条件の試験を行っている。 <Evaluation of minimum dimensions 1>
The minimum dimension of the resist pattern formed in the resist pattern forming example 1 is evaluated. Check if the pattern collapses from the large pattern, and gradually move the observation target to the smaller pattern. The minimum dimension is the pattern immediately before the pattern collapse can be confirmed (the pattern that has not collapsed). The results obtained are shown in Tables 3 and 4.

As shown in Comparative Composition 1, tests are being conducted under conditions where standing waves cannot be completely prevented even with BARC.

<Developer solubility (ADR) evaluation>
Examples Compositions 1, 5, and 7 are each applied to a silicon substrate and soft-baked at 110 ° C. for 60 seconds to prepare a film thickness of 235 nm. After that, the resist film is baked at 100 ° C. for 60 seconds without exposure, and the resist film is paddle-developed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH), and the time until the film dissolves is visually measured. The evaluation results of Example Compositions 1, 5, and 7 are 50 seconds, 33 seconds, and 51 seconds, respectively.

<Preparation Example 9 of Example Composition 9 and Comparative Preparation Example 4 of Comparative Example Composition 4>
Example Composition 9 and Comparative Example Composition 4 are prepared in the same manner as in the preparation of Comparative Composition 1 except that the components are changed as shown in Table 5 below.

<Resist pattern formation example 2>
The surface of a silicon substrate (SUMCO Corp., 8 inches) was first treated with 1, 1, 1, 3, 3, 3-hexamethyl disilazane solution at 90 ° C. for 60 seconds without forming a BARC film. In addition, the resist pattern is formed in the same manner as in the above resist pattern forming example 1 except that the film thickness of the resist film to be formed is set to 800 nm and the light reflectance of the KrF line (248 nm) is 53% by this configuration. To form.

<Evaluation of standing wave reduction 2>
With respect to the resist pattern formed in the resist pattern forming example 2, the standing wave reduction is evaluated in the same manner as the above-mentioned standing wave reduction evaluation 1 except that the pattern corresponding to 300 nm is observed.

<Evaluation of minimum dimensions 2>
Regarding the resist pattern formed in the resist pattern forming example 2, the minimum dimension is evaluated in the same manner as in the evaluation 1 of the minimum dimension. The results obtained are shown in Table 6.

<Preparation of Comparative Example Composition 5>
Solvent B2 (54.53 g) and solvent B3 (23.37 g) are mixed to prepare a B2B3 mixed solvent. To this, 21.539 g of C1-3, 0.052 g of D2, 0.065 g of D3, 0.226 g of D5, 0.129 g of D6, 0.057 g of F2 and 0.033 g of G1 are added, respectively. Mix the solution at room temperature and visually confirm that the solid component dissolves. Comparative Example Composition 5 is obtained.

<Preparation of Example Composition 10>
The Example composition 10 is prepared in the same manner as in the preparation of the comparative composition 5 except that the components are changed as described in the table below.

<Resist pattern formation example 3>
The surface of a silicon substrate (SUMCO Corp., 8 inches) was first treated with 1, 1, 1, 3, 3, 3-hexamethyl disilazane solution at 90 ° C. for 60 seconds without forming a BARC film. The resist pattern is formed as described above, except that the thickness of the resist film to be formed is 800 nm, the light reflectance of the KrF line (248 nm) is 53% by this configuration, and heating is performed after exposure at 110 ° C. for 60 seconds. A resist pattern is formed in the same manner as in Example 1.

<Evaluation of standing wave reduction 3>
With respect to the resist pattern formed in the resist pattern forming example 3, the standing wave reduction is evaluated in the same manner as the above-mentioned standing wave reduction evaluation 1 except that the pattern corresponding to 400 nm is observed. The results obtained are shown in Table 8.

<Evaluation of minimum dimensions 3>
Regarding the resist pattern formed in the resist pattern forming example 3, the minimum dimension is evaluated in the same manner as in the evaluation 1 of the minimum dimension. The results obtained are shown in Table 8.

1. 1. Substrate 2. Resist pattern affected by standing wave 3. Belly 4. Section 5. Distance between abdominal segments 11. Substrate 12. Resist pattern not affected by standing waves

Claims (16)

A method of using a composition comprising a carboxylic acid ester (A) to reduce standing waves in a lithography process:
Here, the carboxylic acid ester (A) is represented by the formula (a).

R ¹ is C _1-10 alkyl, or -OR ¹ ',
R ² is -OR ^2'and
R _{1'and R 2'are independent C 1-20} ^{hydrocarbons ,} respectively.
R ³ and R ⁴ are independently H or C _1-10 alkyl, respectively.
R ¹ and R ³ or R ⁴ or R ² and R ³ or R ⁴ may combine to form a saturated or unsaturated hydrocarbon ring.
n1 is 1 or 2:
However, when n1 = 1, at least ^one of R ¹ or R ^1'and R 2'is a C _3-20 hydrocarbon. The method of claim 1, wherein the composition is applied above the substrate and used to form a film:
Preferably, the composition comprising the carboxylic acid ester (A) is applied without forming the lower antireflection film on the substrate. The method according to claim 1 or 2, wherein the composition comprises a solvent (B):
Preferably, the composition comprises the membranous component (C).
Preferably, the content of the carboxylic acid ester (A) is 1.0 to 200% by mass based on the solvent (B), or preferably, the content of the carboxylic acid ester (A) is based on the filming component (C). The amount is 10 to 3,000% by mass. A lithographic composition comprising a carboxylic acid ester (A) and a solvent (B):
Here, the carboxylic acid ester (A) is represented by the formula (a).

R ¹ is C _1-10 alkyl, or -OR ¹ ',
R ² is -OR ^2'and
R _{1'and R 2'are independent C 1-20} ^{hydrocarbons ,} respectively.
R ³ and R ⁴ are independently H or C _1-10 alkyl, respectively.
R ¹ and R ³ or R ⁴ or R ² and R ³ or R ⁴ may combine to form a saturated or unsaturated hydrocarbon ring.
However, when n1 = 1, at least ^one of R ¹ or R ^1'and R 2'is a C _3-20 hydrocarbon.
Preferably, the solvent (B) comprises an organic solvent (B1);
Preferably, the organic solvent (B1) comprises a hydrocarbon solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, or a mixture thereof. The lithography composition according to claim 4, wherein the carboxylic acid ester (A) is represented by the formula (a1).

here,
R ¹¹ is C _1-5 alkyl and is
R ¹² is a C _3-20 hydrocarbon and is
R ¹³ and R ¹⁴ are independently H or C _1-5 alkyl, respectively. The lithography composition according to claim 4 or 5, further comprising a film forming component (C):
Preferably, the lithographic composition comprises an acid generator (D);
Preferably, the lithographic composition comprises a cross-linking agent (E);
Preferably, the lithography composition comprises the basic compound (F);
Preferably, the lithography composition comprises a surfactant (G); or preferably, the film forming component (C) comprises a polymer (C1);
Preferably, the polymer (C1) has a mass average molecular weight of 500 to 100,000. The lithography composition according to at least one of claims 4 to 6, further comprising an additive (H):
Preferably, the additive (H) comprises a plasticizer, a dye, a contrast enhancer, an acid, a radical generator, a substrate adhesion enhancer, an antifoaming agent, or a mixture thereof. The lithography composition according to any one of claims 4 to 7, wherein the content of the carboxylic acid ester (A) is 1.0 to 200% by mass based on the solvent (B).
Preferably, the content of the carboxylic acid ester (A) is 10 to 3,000% by mass based on the film-forming component (C);
Preferably, the content of the solvent (B) is 10 to 98% by mass based on the lithography composition;
Preferably, the content of the film-forming component (C) is 2 to 40% by mass based on the lithography composition;
Preferably, the content of the acid generator (D) is 0.5 to 20% by mass based on the film-forming component (C);
Preferably, the content of the cross-linking agent (E) is 3 to 30% by mass based on the film-forming component (C);
Preferably, the content of the basic compound (F) is 0.01 to 1.0% by mass based on the membrane-forming component (C); or preferably, the surfactant is based on the membrane-forming component (C). The content of (G) is 0.05 to 0.5% by mass. Assuming that the boiling points of the carboxylic acid ester (A) and the solvent (B) are bp _A and bp _B , respectively, and the saturated vapor pressures at 25 ° C. and 1 atm are vpc _A and vpc _B , respectively.
The lithography composition according to at least one of claims 4 to 8, wherein bp _A > bp _B and vpc _A <vpc _B are satisfied. The lithography composition according to at least one of claims 4 to 9, which is a lithography film forming composition:
Preferably, the lithography composition is a resist composition;
Preferably, the lithography composition is a negative resist composition; or preferably, the lithography composition is a chemically amplified resist composition. Method for manufacturing a membrane including the following steps:
(1) The lithography composition according to at least one of claims 4 to 10 is applied above the substrate;
(2) A film is formed from the lithography composition by depressurization and / or heating:
Preferably, no antireflection film is formed above the substrate before applying the lithography composition. Method for manufacturing a resist pattern including the following steps:
A film is formed from the lithography composition by the method according to claim 11.
(3) Exposing the membrane with radiation;
(4) Develop the film to form a resist pattern:
Here, the lithography composition is a resist composition:
Preferably, light having a wavelength of 13.5 to 365 nm is used for exposure. Method for manufacturing a metal pattern including the following steps:
A resist pattern is formed by the method according to claim 12.
(5a) A metal layer is formed on the resist pattern;
(6a) Remove the remaining resist patterns and the metal layer above them. Method for manufacturing a pattern substrate including the following steps:
A resist pattern is formed by the method according to claim 12.
(5b) Etching with the resist pattern as a mask;
(6b) The substrate is processed. Method for manufacturing a pattern substrate including the following steps:
A resist pattern is formed by the method according to claim 12.
(5c) Etching the resist pattern;
(5d) Etching the substrate:
Here, the combination of the steps (5c) and (5d) is repeated at least twice; and the substrate is composed of a plurality of Si-containing layers laminated, and at least one Si-containing layer is conductive. At least one Si-containing layer is electrically insulating:
Preferably, the conductive Si-containing layers and the electrically insulating Si-containing layers are alternately laminated; or preferably, the resist film formed from the lithography composition has a film thickness of 0.5 to 200 μm. A method for manufacturing a device comprising the method according to at least one of claims 11 to 15.
Preferably, it further comprises the step of forming wiring on the machined substrate; or preferably, the device is a semiconductor device.

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